Process for the catalytic exhaust gas aftertreatment of engine combustion emissions

ABSTRACT

For the regeneration of an NO x  storage catalyst by means of hydrogen in a secondary hydrogen process, the hydrogen required for the regeneration is taken from a primary hydrogen process.

[0001] This application claims the priority of German Patent Document No. 101 61 696.1, filed Dec. 15, 2001, the disclosure of which is expressly incorporated by reference herein.

BACKGROUND AND SUMMARY OF THE INVENTION

[0002] The invention relates to a process for the catalytic exhaust gas aftertreatment of engine combustion emissions by an NO_(x) storage catalyst which can be regenerated by feeding hydrogen to the exhaust gas upstream of the NO_(x) storage catalyst.

[0003] In the case of lean-operated internal-combustion engines, particularly in the case of direct-injection Otto engines, Diesel engines or hydrogen engines, which are operated at an overstoichiometric air-fuel ratio, it is necessary to reduce nitrogen oxides. In addition to continuously operating systems, intermittently operating NO_(x) storage catalysts are used for this purpose which, in an overstoichiometric operation of the internal-combustion engine, intermediately store NO_(x), which can be unloaded again in shorter understoichiometric operating phases. For example, a platinum-containing adsorber is used which oxidizes NO by oxygen first to NO₂. In the subsequent storage step, the acidic NO₂ then attacks a metal oxide and in the process forms the pertaining nitrate. In particular, alkali metals and alkaline earth metals (such as barium) can be used as storage material and, because of their basic characteristics, are capable of forming sufficiently stable nitrates in the given temperature range. When the supply of storage oxides is used up, the engine must be operated for a short time by a rich mixture in order to regenerate the storage device. In this case, the reducing agents present in the rich mixture break up the nitrates and NO is created as well as the original metal oxide.

[0004] In the implementation of this concept, particularly the change from the lean to the rich operation required for the regeneration of the NO_(x) adsorbent is disadvantageous. In addition to the very high control expenditures, there are also the risk of HC and CO leakage as well as a particle/soot emission.

[0005] Remedies were provided by regenerating the NO_(x) storage catalyst by adding hydrogen to the untreated exhaust gas upstream of the NO_(x) storage catalyst. German Patent Document DE 199 39 807 A1 describes such a process and a system for the exhaust gas aftertreatment particularly for lean-mix engines, such as direct-injection Diesel engines and gasoline engines, as well as maintaining the operability of NO_(x) storage catalysts in gasoline and diesel engines and particle filters in diesel engines. For the regeneration of the NO_(x) storage catalyst, hydrogen is intermittently added to the untreated exhaust gas approximately once per minute in order to cause a reduction of the nitrogen oxides. According to German Patent Document DE 199 39 807 A1, a high-expenditure on-board hydrolysis unit is provided for obtaining the hydrogen, which hydrolysis unit, in addition to the actual electrolyzer, comprises a water reservoir, a metering device, a hydrogen reservoir for the intermediate and a piping system.

[0006] This unit requires the costs of a separate hydrogen process that includes the process-related devices required exclusively for the regeneration of the NO_(x) storage catalyst. The hydrogen used for the regeneration of the NO_(x) storage catalyst has to be made available only for the purpose of regenerating the catalyst and, if required, has to be intermediately stored in a hydrogen reservoir. The water reservoir has to be refilled regularly.

[0007] It is therefore an object of the invention to provide a process which overcomes the above-mentioned disadvantages.

[0008] According to the invention, this object is achieved by using a process which includes the removal of the hydrogen used in a secondary process for the regeneration of the NO_(x) storage catalyst from a primary hydrogen process.

[0009] Within the scope of the invention, the term “hydrogen” also applies to a hydrogen-rich synthesis gas.

[0010] In the case of a motor vehicle, whose internal-combustion engine can be operated with hydrogen, it is very expedient for a partial quantity to be removed from the hydrogen flow fed to the internal-combustion engine and to be fed to the exhaust gas flow upstream of the NO_(x) storage catalyst. Depending on the further development of the exhaust gas aftertreatment device, the feeding of the hydrogen to the exhaust gas flow takes place discretely or continuously.

[0011] If, in a primary hydrogen process, hydrogen fuel for an engine, particularly of a fuel cell, is generated by a reformer, it is very advantageous for a partial quantity to be removed from the primary hydrogen process discretely or continuously depending on the need of the emission control device and to be fed to the exhaust gas flow upstream of the NO_(x) storage catalyst.

[0012] Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013]FIG. 1 is a schematic view of an example of the regeneration of an NO_(x) storage catalyst comprising an adsorber part in the case of a motor vehicle whose internal-combustion engine can be operated with hydrogen;

[0014]FIG. 2 is a schematic view of an example of the regeneration of an NO_(x) storage catalyst comprising two adsorber parts arranged in parallel in the case of a motor vehicle whose internal-combustion engine can be operated by hydrogen;

[0015]FIG. 3 is a schematic view of an example of the reaction processes taking place in a reformer system;

[0016]FIG. 4 is a schematic view of an example of the regeneration of an NO_(x) storage catalyst by hydrogen in the case of a motor vehicle which comprises a reformer; and

DETAILED DESCRIPTION OF THE DRAWINGS

[0017]FIG. 1 describes the regeneration of an NO_(x) storage catalyst for a motor vehicle whose internal-combustion engine can be operated with hydrogen in a primary hydrogen process. For the storage of the fuel, an insulated tank 11 is provided in which cryogenic hydrogen is stored in the liquid state at approximately −260° C. Through pipes 12, 12 c, the hydrogen reaches the internal-combustion engine 14 and is converted there by air fed through the pipe 13. The nitrogen oxides, which are contained in the exhaust gas 15 in the lean-mix operation in an overstoichiometric combustion, are fed to an NO_(x) storage catalyst 18, and the cleaned exhaust gas is removed by way of a pipe 19.

[0018] A portion of the hydrogen fed to the internal-combustion engine 14 through the pipe 12 is branched off in a pipe 12 a and is fed in the exhaust gas flow above the NO_(x) storage catalyst 18 to a secondary hydrogen process for the purpose of regenerating the storage device. The hydrogen is stored in the tank 11 in the liquid state, while it reacts in the catalyst in the gaseous state. If the hydrogen is fed in a liquid state through insulated pipes 12, 12 c to the internal-combustion engine 14, it is advantageous for the branched-off hydrogen to be evaporated in the pipe 12 a, so that it is added in the gaseous state to the exhaust gas flow 15 above the catalyst 18. The evaporation of the hydrogen can be achieved in that the pipe 12 a is in a heat-exchanging contact with another pipe carrying a warmer medium. The pipe 12 a extends, for example, in a spiral shape around another pipe or is surrounded by another pipe in a spiral shape. A further development with cooling ribs is also expedient for warming up the hydrogen with air.

[0019] In the adsorption operation the NO_(x) storage catalyst cleans nitrogen oxides from the exhaust gas by first oxidizing NO by oxygen at the platinum of the catalyst to NO₂, and subsequently the acidic NO₂ corresponding to a storage attacks a metal oxide while forming the pertaining nitrate. As the loading of the NO_(x) storage catalyst increases, the supply of storage oxides is applied so that their regeneration is required. This is achieved by feeding hydrogen, and the hydrogen and the stored nitrogen oxides react according to the following equation into nitrogen and water:

H₂+1/x NO_(x ads)=>½×N₂+H₂O  (1)

[0020] In this case, the controlling of the hydrogen feed takes place such that a regeneration occurs as a function of the loading condition of the catalyst. A high loading of the NO_(x) storage catalyst necessitates a high hydrogen addition to the untreated exhaust gas. When the loading decreases, the hydrogen feed is correspondingly discretely or continuously reduced and vice-versa.

[0021]FIG. 1 illustrates an embodiment in which the NO_(x) storage catalyst comprises an adsorber part 18 which, in areas, can be operated alternately in the adsorption or the desorption operation. For this purpose, the hydrogen is fed, preferably continuously, to the exhaust gas flow above the NO_(x) storage catalyst 18 so that areas which change successively with respect to time are acted upon by hydrogen. As a result of the regeneration of these areas, the regeneration of the entire storage catalyst 18 takes place. For example, at a point in time t₀, an area 18 a is acted upon by hydrogen and, at a point in time (t₀+Δt), an area 18 c is acted upon by hydrogen. While the area 18 b, 18 d continues to adsorb NO_(x) at the corresponding point in time. For the admission of hydrogen to partial areas 18 a, 18 c of the cross-section 18, for example, a covering element is used which can be rotated relative to the catalyst body and which divides the circular absorber part 18 into sectors and, with which, the added hydrogen can be directed to certain areas. According to another embodiment, the nozzle for charging the hydrogen can be moved so that a targeted charging takes place.

[0022]FIG. 2 shows an alternative further embodiment comprising an NO_(x) storage catalyst which has two adsorber parts 28 a, 28 b arranged in parallel. The exhaust gas flow, which contains nitrogen oxides and is discharged through the pipe 25 from the internal-combustion engine 24, can be guided through the pipes 25 a, 25 b through the adsorber part 28 a and/or through the adsorber part 28 b; hydrogen can be fed through the pipes 22 a, 22 b to the exhaust gas flow above the catalyst 28.

[0023] As a result of the operations of the adsorber parts 28 a, 28 b which change successively with respect to time, in the adsorption or desorption operation, a regeneration of one adsorber part can take place in each case, while the other continues to be available for the cleaning of the exhaust gas. Thus, at the point in time t₀, the adsorber part 28 b is regenerated by the feeding of hydrogen by way of the pipe 22 b, which is illustrated as a solid line, to the untreated exhaust gas, while the adsorber part 28 a continues to adsorb nitrogen oxides from the exhaust gas fed by way of the pipe 25 a illustrated as solid line 25 a. At a subsequent point in time t₀+Δt, the adsorber part 28 a is acted upon by hydrogen by way of the pipe 22 a illustrated by a broken line so that its regeneration takes place, while the adsorber part 28 b adsorbs nitrogen oxides from the exhaust gas. Subsequently, at a point in time t₀+2 Δt, both adsorber parts 28 a, 28 b are regenerated and are available for cleaning the exhaust gas.

[0024] Furthermore, it is very expedient to use the process according to the invention in the case of a motor vehicle which, in a primary hydrogen process, comprises a fuel cell and which, for supplying the latter with hydrogen, comprises a reformer, as illustrated, for example, in FIG. 3. The internal-combustion engine of the motor vehicle is expediently operated by hydrocarbon which is also available to the reformer for producing a hydrogen-rich synthesis gas. Corresponding to the respective type of reforming, hydrocarbon-containing fuel 32 is reacted in the reformer 30 in a reaction zone 36 b with the addition of air 33 and/or water 311 to a reformate including predominantly H₂, CO and N₂.

[0025] An emission control device of a motor vehicle of this type is illustrated in FIG. 4. A hydrocarbon-containing fuel, such as gasoline or Diesel fuel, is stored in a tank 41, which fuel is fed to an internal-combustion engine 44 by way of pipes 42, 42 a. The exhaust gas, which is generated during the combustion with air fed by way of the pipes 43, 43 a and which contains nitrogen oxides in the lean-mix operation, is fed to an NO_(x) storage catalyst 48 by way of the pipe 45 for cleaning, which NO_(x) storage catalyst is regenerated in that alternately areas 48 a, 48 c are acted upon by hydrogen, while areas 48 b, 48 d continue to be available for the cleaning of the exhaust gas. The adsorption and desorption operations continue to correspond to those shown in FIG. 1.

[0026] The hydrogen required in a secondary hydrogen process for the regeneration of the NO_(x) storage catalyst 48 according to Equation (1) is branched off from the reformate provided to a fuel cell which is not shown in this representation. For reforming the hydrogen, hydrocarbon-containing fuel is fed to the reformer 46 by way of the pipe 42 b, as well as, air and/or water is/are fed by way of the pipes 43 b, 411, 412; by way of pipe 47, the reformate is added to the exhaust gas flow above the NO_(x) storage catalyst 48 for the purpose of regeneration. The cleaned exhaust gas is carried away by way of a pipe 49, 49 b, in which case it is very expedient to guide at least a partial flow by way of a pipe 49 a, for the purpose of recovering water through a condenser 49 c. Also in this embodiment, naturally—as illustrated and described by FIG. 2—an NO_(x) storage catalyst 48 can be used which has two adsorber parts. 

What is claimed:
 1. A process for catalytic exhaust gas aftertreatment of engine combustion emissions with an NOx storage catalyst which can be regenerated by feeding hydrogen to the exhaust gas upstream of the NOx storage catalyst, the process comprising feeding the hydrogen used in a secondary process for the regeneration and desorption of the NOx storage catalyst or adsorber catalyst from a primary hydrogen process. 2 The process according to claim 1, wherein, in the case of a motor vehicle whose internal-combustion engine can be operated in a primary hydrogen process with hydrogen, removing a partial quantity of hydrogen from the hydrogen flow fed to the internal-combustion engine and feeding the partial quantity to the exhaust gas flow upstream of the NOx storage catalyst.
 3. The process according to claim 1, wherein, in the case of a motor vehicle whose internal-combustion engine can be operated with hydrocarbon and in the case of which, with a reformer, hydrogen is generated from hydrocarbon for the operation particularly of a fuel cell in a primary hydrogen process, removing a partial quantity of hydrogen from the primary process and feeding the partial quantity to the exhaust gas flow upstream of the NOx storage catalyst.
 4. The process according to claim 3, further comprising, downstream of the NOx storage catalyst, condensing water vapor contained in the exhaust gas and feeding it to a hydrogen process.
 5. The process according to claim 1, further comprising, downstream of the NOx storage catalyst, condensing water vapor contained in the exhaust gas and feeding it to a hydrogen process.
 6. The process according to claim 4, further comprising alternating two parallelly arranged adsorber parts of the NOx storage catalyst in a successive manner with respect to time, through which adsorber parts the flow takes place in the adsorption or desorption operation.
 7. The process according to claim 1, further comprising alternating two parallelly arranged adsorber parts of the NOx storage catalyst in a successive manner with respect to time, through which adsorber parts the flow takes place in the adsorption or desorption operation.
 8. The process according to claim 3, further comprising regenerating different areas of an adsorber part of the NOx storage catalyst in a successive manner with respect to time.
 9. The process according to claim 1, further comprising regenerating different areas of an adsorber part of the NOx storage catalyst in a successive manner with respect to time.
 10. An engine exhaust system comprising: an NOx storage catalyst which is regenerable by feeding hydrogen to the exhaust gas upstream of the NOx storage catalyst, wherein hydrogen is fed from a primary hydrogen process to a secondary process for the regeneration and desorption of the NOx storage catalyst or adsorber catalyst. 11 The system according to claim 10, wherein, in the case of a motor vehicle whose internal-combustion engine can be operated in a primary hydrogen process with hydrogen, a partial quantity of hydrogen is removed from the hydrogen flow fed to the internal-combustion engine and fed to the exhaust gas flow upstream of the NOx storage catalyst.
 12. The system according to claim 10, wherein, in the case of a motor vehicle whose internal-combustion engine can be operated with hydrocarbon and in the case of which, with a reformer, hydrogen is generated from hydrocarbon for the operation particularly of a fuel cell in a primary hydrogen process, a partial quantity of hydrogen is removed from the primary process and fed to the exhaust gas flow upstream of the NOx storage catalyst.
 13. The system according to claim 12, wherein, downstream of the NOx storage catalyst, water vapor contained in the exhaust gas is condensed and fed to a hydrogen process.
 14. The system according to claim 10, wherein, downstream of the NOx storage catalyst, water vapor contained in the exhaust gas is condensed and fed to a hydrogen process.
 15. The system according to claim 12, wherein the NOx storage catalyst includes two parallelly arranged adsorber parts, through which the flow takes place in the adsorption or desorption operation, the adsorber parts being alternately operated in a successive manner with respect to time.
 16. The system according to claim 10, wherein the NOx storage catalyst includes two parallelly arranged adsorber parts, through which the flow takes place in the adsorption or desorption operation, the adsorber parts being alternately operated in a successive manner with respect to time.
 17. The system according to claim 12, wherein the NOx storage catalyst includes an adsorber part having different areas, the different areas being regenerated in a successive manner with respect to time.
 18. The system according to claim 10, wherein the NOx storage catalyst includes an adsorber part having different areas, the different areas being regenerated in a successive manner with respect to time. 